Method of treating nickel-copper alloys and products resulting therefrom



Patented Mar. 7, 1939 PATENT OFFICE METHOD OF TREATING NICKEL-COPPERALLOYS AND THEBEFROM PRODUCTS RESULTING Augustus Ernest Kayes,Huntington, W. Va., as-

signor to The International Nickel Company, Inc., New York, N. Y., acorporation of Delaware m. Drawing. Application April 19, 1935, SerialNo. 17,258. Renewed August 9, 1938 13 Claims.

The present invention relates to a method of improving nickel and nickelalloys and to the improved product resulting therefrom.

Heretofore it has been customary in the deoxidation of nickel and nickelalloys, particularly nickel-copper alloys, to add a small quantity(about 0.05 to about 0.15%) of magnesium in conjunction with certainpreliminary deoxidizers, each as manganese and aluminum. These agentswere added for the purpose of counter-acting the harmful effects ofsulphur and oxides contained in the metal which rendered the metalnonmalleable and which tended to cause unsound ingots, if not properlytaken care of. Although various proposals have been made to overcome theprior disadvantages, none, as far as I am aware, has been whollysatisfactory, practical and acceptable when carried into commercialpractice on an industrial scale.

I have discovered that the incorporation of small quantities ofzirconium alone or together with phosphorus or boron to the melt ofnickel or nickel alloys, especially in conjunction with magnesium and insome cases aluminum, improves the hot malleability of the metal,particularly a nickel-copper alloy and renders'it less red short. Incarrying the invention into practice, I have found that zirconium may beintroduced through the slag on the surface of the molten metal, orplunged into the metal in the furnace, or may be added in the ladle.'The quantity of zirconium necessary to accomplish the new results ofproviding hot malleability and less red shortness varies and dependsupon the impurities and substances with which the melt is contaminated.For general purposes, it has been found that about 0.01 to about 0.25%ofzirconium alone or together with combinations of .005 to 15% ofphosphorus, or 0.003 to 0.02% of boron will give satisfactory resultswhen added to a melt of nickel or nickel alloys, particularly when usedin conjunction with about 0.05 to about 0.20% of aluminum and about 0.02to about 0.15% of magnesium.

For the purpose of giving those skilled in the art a betterunderstanding of the invention, the following illustrative specificexamples will be given:

Nickel I have found that improved nickel may be produced by treating amelt of nickel either carbonfree or carbon bearing with zirconium aloneor zirconium with phosphorus or boron in conjunction with magnesium. Thefollowing schedule indicates the range in percent and the preferredpercent of the aforesaid agents to be used in the treatment of nickel.

It is preferred to add the agents to the nickel melt in the followingorder: zirconium, magnesium, and phosphorus or boron. The additions aremade to the melt either in a furnace or in a ladle after tapping fromthe furnace and before teeming into ingot molds. Satisfactory resultshave been obtained by having the temperature of the melt at the time ofthe addition at about 2800" F. to about 3000 F.

The treatment of a melt of nickel with airconium, magnesium, andphosphorus or boron in controlled amounts will eliminate or counteractdetrimental effects due .to the presence of impurities, contaminationsand deleterious traces encountered in the general refining of nickel andwill produce an improved product having no red short range and one whichis malleable at all temperatures up to about 2300 F. or about 2500 F.The improved nickel in ingot form can be suitably overhauled, hot and/orcold worked to produce rods, bars, sheets and strip without difficultyand to give a ductile product free from seams.

It is to be noted that the mesence of detrimental elements orconstituents in nickel, such as sulfur, selenium, tellurium, refractoryparticles like silicates and oxides, etc., cause red shortness or a lackof hot malleability at hot forging and rolling temperatures. In priorpractice, manganese, aluminum and magnesium were used to counteract thedetrimental elements, etc. I have found that the reaction products ofaluminum and magnesium including silicates and oxides remained in themelt as non-metallic inclusions and were harmful due to their harmfulcontribution to red shortness and to the formation of seams. By theutilization of the present treatment, the aforesaid difficulties can beovercome and an improved product can be produced.

Nickel-copper alloys In the treatment of nickel-copper alloys,particularly those containing more than 50% of nickel, "red shortnessmay be eliminated and a sound and malleable metal may be produced. Thusa nickel-copper alloy having about to nickel and about 23 to 35% ofcopper as the principal components may be treated in accordance with theprinciples of the present invention to eliminate, remedy or counteractthe effect of detrimental constituents. In carrying the invention intopractice, it is preferred to use zirconium in conjunction withphosphorus. These, agents are used in conjunction with aluminum andmagnesium in the following percentages:

The aforesaid elements are preferably added in sequence. Thus, aluminumis first added to the melt under treatment, zirconium second, magnesiumthird and phosphorus last. The addition of these agents may be madeeither in the furnace or in the ladle. In practice satisfactory resultshave been obtained by having the temperature of the molten metal at thetime of the treatment within a range of about 2700 F. to about 2900 .F.

It has been found that the combination of the aforesaid agents can bevaried depending upon the nature and kind of impurities in the moltenmetal. In some cases, magnesium may be omitted if the melt issubstantially free from sulphur.

After the foregoing treatment, the treated nickel-copper alloys can beteemed into ingot molds. The ingots can then be overhauled in accordancewith customary practice. After overhauling, the ingot may be submittedto hot and/or cold working to produce rods, bars, sheet, strip, etc.,without any difficulty due to red shortness, since the alloy ismalleable at all temperatures up to about 2250 F. to about 2350 F. Thisnew result is a distinct improvement over prior procedures whichproduced nickelcopper alloys which were not commercially malleable forhot working at temperatures below about 1600 to 1700 F.

Nickel-iron-chromium alloys The present invention may be used for thetreatment of an alloy containing about 50 to about of nickel, about0.25% to about chromium alloy has improved malleability over practicallythe entire high temperature range.

In carrying the invention into practice, a nickel-lron-chromium alloycontaining 80% nickel, 6% iron, 14% chromium and less than 0.15% carbonis deoxidized with agents such as aluminum and/or magnesium. After thistreatment, about 25% of zirconium and about .01% of boron is added tothe melt. The malleableizing elements are thoroughly distributedthroughout the melt which is then tapped and teemed. In certaininstances, it may be desirable to add a the malleabilizing elementszirconium and boron to the melt in the ladle instead of in the furnace.Satisfactory results have been produced by the present treatment andalloys have been made which are sound and free from blow holes,substantially free from seams or splits or cracks and substantially freefrom red shortness". The

alloys can now be hot worked without any dimculties due to redshortness" down to a temperature of about 1400 F.

. Nickel-manganese allows It has been found that alloys containingnickel and manganese can be treated by the present invention. Thus,nickelanese alloys containing about 1 to about 20% of manganese can betreated with zirconium, magnesium and phosphorus or zirconium, magnesiumand boron to eliminate the effects of detrimental oonstitutents and toproduce an improved alloy.

In c ying the invention into practice, a melt of the nickel-manganesealloy may be treated with zirconium first, magnesium second andphosphorus or boron third. The treatment may be made either in thefurnace orin the ladle after tapping from the furnace and before teeminginto the ingot mold. It has been found that it is preferred to have thetemperature of the melt at the time of the addition within the range of2800 F. to about 3000" 1-. The agents may be used in amounts set forthin the following schedule:

Agent Bangs mm Percent Percent Zirconium 0.01 -0.25 0.06 m1 m 0. 02 -0.l5 0. 0G Phosphorus 0. 01 -0. 06 0. 015' Boron 0. (KB-(L 02 0. (I

The present treatment has resulted in improved products havingpractically no red short" range and c a commercial malleability at alltemperatures up to about 2300 to about 2500 F. It has been found'thatnickel manganese alloys in ingot form can be suitably overhauled, hotand/or cold worked to produce rods, bars, sheet and strip withoutdefects. Ductile products substantially free from seams have beenobtained.

For the purpose of controlling the addition of a malleableizing elementto a melt under treatment and determining the sufllciency of suchaddition, use is made of the "hammer and anvil" test. In conducting thistest, a spoonful (about 3 to 5 lbs.) of melted metal is removed from thefurnace and a test bar (about x 1%" x 6" and about 1 lb.) is poured. Thesolidified test bar is hammered with a sledge hammer (about 10 lbs.). Inthe event cracks develop, the metal is Judged to be "red short. Afurther controlled addition of malleableizing element is made to themelt and another test bar is made and tested. This procedure is repeateduntil the test bar withstands the hand forging operation withoutcracking. The melt is then treated properly and is poured into the mold.

In industrialpractice, it is to be noted that a series of hightemperature bend tests are conducted on material from each melt afterthe melt has been cast into-ingots and before it is further processed.Thue tests provide a means of measuring the hot ductility and thuspredicting the rolling quality of the material. In conducting bendtests, a forged bar 55" thick by 1" wide by 6" long is heated in anelectrically controlled furnace to a predetermined temperature. It isthen withdrawn from the furnace and bent 180 degrees with a single blowof a steam hammer. If the test piece withstands this deformation withoutcrackingitk asgood; ifnot,itis

called bad. This test is repeated at intervals of 100 F. over the rangefrom 1200' F. to 2300 F.-2500 F. The dimensions of the bend testspecimens havebeen so chosen that a good bend at any temperatureindicates that the material is capable of being hot worked at thattemperature without cracking.

I claim:

1. In the process of treating a mass of conventionally deoxidized and,malleableized nickel and nickel alloys having red shortness to renderthe same substantially free from seams and from red shortness thatimprovement which comprises treating a mass of the aforesaid characterwhile molten and after conventional deoxidizing and malleableizingtreatments with a controlled, critical and small amount of zirconium anda member of the group consisting of boron and phosphorus to render saidmass, when solidified,

substantially free from seams and from red shortness and to impartmalleability to said nickel mass, when solidified, from the hotmalleable zone to the cold malleable zone.

2. In the process of treating a mass of conventionally deoxidized andmalleableized nickel and nickel alloys having red shortness to renderthe same substantially free from seams and from red shortness thatimprovement which comprises treating a mass of the aforesaid characterwhile molten and after conventional deoxidizing and malleableizingtreatments with a controlled, critical and small amount within a rangeof about 0.003% to about 0.75% of zirconium and a member of the groupconsisting of boron and phosphorus to render said mass, when solidified,substantially free from seams and from red shortness and to impartmalleability to said nickel mass, when solidified, from the hotmalleable zone to the cold malleable zone.

3. In the process of treating a mass of conventionally deoxidized andmalleableized nickel and nickel alloys having red shortness to renderthe same substantially free from seams and from red shortness thatimprovement which comprises treating a mass of the aforesaid characterwhile molten and after conventional deoxidizing and malleableizingtreatments with a controlled, critical and small amount of zirconium anda member of the group consisting of boron and phosphorus to render saidmass, when solidified, substantially free from seams and from redshortness and to impart malleability to said nickel mass, whensolidified, from the hot malleable zone to the cold malleable zone, thesaid zirconium, boron and phosphorus being used within a range of about0.010% to about 0.25%, about 0.003% to about 0.020%, and about 0.01% toabout 0.05%, respectively.

4. The process of treating a mass of malleable nickel and nickel alloyshaving red shortness to -ender the same substantially free from seamsand from red shortness which comprises adding to a mass of the aforesaidcharacter while molten a controlled and restricted amount of zirconiumand a member of the group consisting of boron and phosphorus to rendersaid mass, when solidified, substantially free from seams and from redshortness andto impart malleability to said nickel mass, whensolidified, from the hot malleable zone to the cold malleable zone,determining the sufiiciency of the controlled and restricted amount ofthe agent on test samples by the hammer and anvil test while the mass ismaintained molten, and continuing the aforesaid operations until thehammer and anv test determines the sufficien- 3 cy of the controlled andrestricted amount of the agent added to render the nickel mass, whensolidified, substantially free from seams and red shortness and toimpart malleability to said nickel mass, when solidified, from the hotmalleable zone to the cold malleable zone.

5. The process of treating a mass of malleable nickel and nickel alloyshaving red shortness to render the same substantially free from seamsand from red shortness which comprises treating a mass of the aforesaidcharacter while molten with a controlled and restricted amount ofzirconium and a member of the group consisting of boron and phosphorusto render said mass. when solidified, substantially free from seams andfrom red shortness and to impart malleability to said nickel mass, whensolidified, from the hot malleable zone to the cold malleable zone,subjecting samples of said molten mass to a physical test to determinethe sufficiency of the aforesaid treating operation, and repeating theaforesaid test after further treatment of said nickel mass with at leastone of the aforesaid agents until the nickel mass is rendered, whensolidified, substantially free from seams and from red shortness and isrendered malleable from the hot malleable zone to the cold malleablezone.

6. A treated nickel mass having such a constitution as to be malleablefrom the hot malleable zone to the cold malleable zone and as to possessstrength, and rendered substantially free from seams and red shortnessand rendered malleable from the hot malleable zone through theconventional red short zone to the cold malleable zone by a controlledand restricted amount of zirconium within a range of about 0.010% toabout 0.25% and a member of the group consisting of boron and phosphoruswithin a range of about 0.003% to about 0.75%.

7. A treated nickel mass having such a constitution as to be malleablefrom the hot malleable zone to the cold malleable zone and as to possessstrength, and rendered substantially free from seams and red shortnessand rendered malleable from the hot malleable zone through theconventional red short zone to the cold malleable zone by a controlledand restricted amount of zirconium and a member of the group consistingof .boron and phosphorus, the zirconium, boron and phosphorus being usedwithin a range of about 0.010% .to about 0.25%, about 0.003% to about0.020%, and about 0.01% to about 0.05%, respectively.

8. The process of treating a mass of malleable nickel and nickel alloyshaving red shortness to render the same substantially free from seamsand from red shortness which comprises subjecting a mass of theaforesaid character while molten to a preliminary treatment withconventional deoxidizing and malleableizing agents including about 0.05to about 0.20% of aluminum, and about 0.02 to about 0.15% of magnesiumto produce a conventionally deoxidized and malleabilized nickel masspossessing conventional red shortness, adding to the thus-treated massof the aforesaid character while molten a controlled and restrictedamount of zirconium and a member of the group consisting of boron andphosphorus to render said mass, when solidified, substantially free fromseams and from red shortness and to impart malleability to said nickelmass, when solidified, from the hot malleable zone to the coldmalleablev zone, determining the suificiency of the controlled andrestricted amount of the agent on test samples by the hammer and an testwhile the mass is maintained molten, and continuing the aforesaidoperations until the hammer and anvil" test determines the suiiiciencyoi the.

tional deoxidizing and malleableising agents ineluding aluminum andmagnesium to produce a conventionally deoxidisedand malleabilized nickelmass possessing conventional red shortness, treating the thus-treatedmass oi the aforesaid character while molten with a controlled andrestricted amount oi zirconium and a member of the group consisting ofboron and phosphorus to render said mass, when solidifled, substantiallyfree from seams and from red shortneu and to impart malleability to saidnickel mass, when solidifled, from the hot malleable zone to the coldmalleabie zone. subjecting samples of said molten mass to a physicaltest to determine the suiliciency oi the aforesaid treating operation,and repeating the aforesaid test after further treatment of said nickelmass with at least one of the aforesaid agents until the nickel mass isrendered, when solidified, substantially tree from seams and from redshortness and is rendered malleable from the hot malleable zone to thecold malleable zone.

10. As an article of manufacture, an improved ductile nickel mass 01'the group of materials consisting oi malleable nickel and malleablenickel alloys having a structure substantially free from defectsincluding seams, cracks and the like and having a constitution resultingfrom conventional deoxidizing and malleablelzing operations and fromasubsequent treatment with a controlled,

restricted and critical amount of zirconium and.

of a member of the group of boron and phosphorus, the said nickel massbeing substantially free from conventional red shortness and possessingmalleability from the hot malleable zone to and into the cold malleablezone and having been worked through the conventional red short zone attemperatures below about 1600 1". to about 1700 F.

11. As an article of manufacture, an improved ductile nickel mass of thegroup oi materials connickel mass being substantially free fromconventional red shortness and possessing malieability from the hotmalleable zone to and into the cold malleable zone and having beenworked 1 through the conventional red short zone at temperatures belowabout 1600" F. to about 1700 F.

12. As an article of manufacture. an improved ductile nickel masscomprising a malleable nickelcopper alloy having a structuresubstantially free from defects including seams, cracks and the like andhaving a constitution resulting from conventional deoxidizing andmalleableizing operations and irom a subsequent treatment with acontrolled, restricted and critical amount of zirconium and of a memberof the group consisting of boron and phosphorus, the said nickel massbeing substantially free from conventional red shortness and possessingmalleability from the hot malleable zone to and into the cold malleablezone and having been worked through the conventional red short zone attemperatures below about 1600 F. to about 1700 F.

13. As an article of manufacture, an improved ductile nickel masscomprising a malleable nickelcopper alloy having a structuresubstantially tree from defects including seams, cracks and the like andhaving a constitution resulting from conventional deoxidizing andmalleableizing operations and from a subsequent treatment with acontrolled, restricted and critical amount 01 zirconium and a member ofthe group consisting of boron and phosphorus, the said zirconium, boronand phosphorus being used within a range 01' about 0.01% to about 025%,about 0.003% to about 0.020%, and about 0.01% to about 0.05%,respectively, the said nickel mass being substantially tree fromconventional red shortness and possessing malleability from the hotmalleable zone to and into the cold malleable zone and having beenworked through the conventional red short zone at temperatures belowabout 1600 F. to about 1700 F.

AUGUSTUS ERNEST KAYES.

